JP2005274743A - Seamless belt, manufacturing method for belt, electrophotographic apparatus using it and coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a seamless belt preventing defects occurring on a surface (surface defects) such as a bumpy surface or cracked patterns and with good detachability made of smooth and homogeneous film state polyimide or polyamidoimide with uniform dispersion of inorganic filler and no residual air bubbles, in the seamless belt for electrophotography. <P>SOLUTION: In the seamless belt formed by using a coating liquid containing inorganic filler and polyimide or polyamidoimide, the coating liquid contains the inorganic filler, polyimde precursor or polyamidoimide precursor, organic polar solvent and polyoxyethylene alkyl phenyl ether modified silicone. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a seamless belt, and moreover, a seamless belt suitably used for a belt constituting part preferably provided in an electrophotographic apparatus such as a copying machine or a printer, a method for producing the belt, and an electrophotography using the belt The present invention relates to an apparatus and a coating liquid.

  Conventionally, a solution containing a polyimide precursor or a polyamideimide precursor is applied and cast on a support (molding mold: rotating body, belt, etc.) to form a coating film, and then the precursor is heated to form an imide. In the process of accelerating the process, the surface of the thin film generates a yuzu skin or tortoise shell pattern (hereinafter abbreviated to yuzu skin or tortoise shell pattern), or is familiar with the substrate material to be coated when applying a solution. However, it is known to cause defects due to repelling.

  In order to improve such problems, for example, the following methods have been proposed. It has been proposed to prevent itching by adding a fluorosurfactant to a polyimide, polyamideimide or polyamic acid solution (see, for example, Patent Document 1).

  It has also been proposed to prevent repelling by including a surfactant containing a siloxane unit in the polyimide precursor solution (see, for example, Patent Document 2).

  Alternatively, by adding a fluorosurfactant to a heat-resistant resin (polyimide resin, polyamideimide resin, polyamide resin) solution in which a filler is dispersed, repelling at the time of coating to a substrate (made of tetrafluoropolyethylene), etc. It has been proposed to prevent (see, for example, Patent Document 3).

  Furthermore, in order to form a semiconductive polyimide endless belt (two-layer structure), a conductive material such as carbon and a solution containing a polyimide precursor are mixed with a fluorosurfactant as a compatibilizing agent to make the conductivity. It has been proposed to increase the dispersion uniformity of substances (for example, see Patent Document 4).

  According to each of the above proposals, it is possible to avoid the generation of the yuzu skin and the turtle shell pattern and to suppress the repelling. However, a thick film (for example, 50 μm or more) film containing an inorganic filler is a solution (coating liquid) containing a polyimide precursor or a polyamideimide precursor, an inorganic filler, and a solvent (for example, N-methylpyrrolidone). ) (For example, centrifugal molding method), it is necessary to increase the viscosity of the coating liquid and to increase the concentration of the solid content. Alternatively, although the repelling can be improved, bubbles are likely to be generated in the coating liquid preparation process in which the inorganic filler is dispersed, the coating liquid application process, and the like, and the generated bubbles are not easily removed. For this reason, the problem that bubbles remain in the coating film (coating film) to cause defects occurs.

  Moreover, in the use of this invention, in order to provide an electrical resistance and heat conductivity, it is necessary to fill with an inorganic filler, and this dispersibility also becomes a problem. Although this point is also described in the previous Patent Document 4, the above-mentioned problem remains. In particular, carbon black is preferably used as the electric resistance adjusting agent. Generally, as a method for improving the dispersibility of carbon black, a method of treating carbon black with a coupling agent (see, for example, Patent Documents 4 to 8). However, in the coating liquid of the present invention, there is a problem that dispersion is still incomplete by this method and the cost is high.

  There is also a method of grafting monomer components in the presence of carbon black (see, for example, Patent Documents 9 and 10), but this method has poor grafting efficiency. In the coating liquid of the present invention, grafting is not possible. The subsequent dispersion of carbon black was insufficient. Moreover, even if the dispersibility in the solution is improved, the surface properties are often disturbed by aggregation during the formation of the coating film.

Further, as a method for producing a polyimide or polyamideimide seamless belt, a molding method in which a coating solution is applied to the inner surface of a cylinder to form a film is used. In this construction method, it is necessary to peel the coating film from the cylindrical mold after the final baking, and usually, the mold inner surface is often subjected to a treatment that is easy to release. However, since the final baking is performed at a high temperature of 250 ° C. or higher, the release layer is not durable and the manufacturing cost is high. Further, some materials that satisfy the characteristics of the present invention cannot be peeled off.
Japanese Patent Publication No. 5-8222 JP 2001-302913 A JP 2001-123066 A JP 7-156287 A JP-A 63-175869 Japanese Patent Laid-Open No. 63-158666 British Patent No. 1583564 GB 1583411 Specification JP-A 64-6965 German Patent No. 3102823

  The present invention has been made in consideration of the above-described circumstances, and prevents defects (surface defects) generated on the surface such as a yuzu skin and a turtle shell pattern, and at the same time, the inorganic filler is uniformly dispersed and bubbles remain. It is obtained by efficiently peeling a seamless belt made of polyimide or polyamideimide in a smooth and homogeneous film state from a mold. Further, the present invention provides a seamless belt used for a belt constituting portion equipped in an electrophotographic apparatus, a seamless belt manufacturing method, a coating liquid used therefor, and a belt constituting portion using the seamless belt (in particular, intermediate transfer). It is an object to provide an electrophotographic apparatus equipped with a belt.

  As a result of intensive studies, the present inventors use a coating liquid containing polyoxyethylene alkylphenyl ether-modified silicone in an organic polar solvent solution of a polyimide precursor or polyamideimide precursor in which a filler is dispersed. Thus, the present inventors have found that the above problem can be improved even when a thick film (for example, 50 μm or more) coating film (for example, centrifugal molding) is formed by coating and casting on a support.

  In order to solve the above-mentioned problem, the invention according to claim 1 is a seamless belt obtained by using a coating liquid containing a filler and polyimide or polyamideimide, wherein the coating liquid comprises a filler, a polyimide, A seamless belt comprising a precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone.

  The invention according to claim 2 is characterized by the seamless belt according to claim 1, wherein the content of the polyoxyethylene alkylphenyl ether-modified silicone is 0.005 to 1.0 wt% of the coating solution. .

  The invention described in claim 3 is characterized in that the seamless belt has a film thickness of 50 μm or more.

  According to a fourth aspect of the present invention, there is provided a seamless belt for a belt constituent part provided in an electrophotographic apparatus for transferring a toner developed image formed on an image carrier and forming an image on a recording medium. The belt is characterized by the seamless belt according to any one of claims 1 to 3.

  According to a fifth aspect of the present invention, a plurality of color toner developed images sequentially formed on an image carrier are sequentially superimposed on an intermediate transfer belt to perform primary transfer, and the primary transfer images are batch-recorded on a recording medium. In the seamless belt for a belt constituting part equipped in the electrophotographic apparatus for secondary transfer, the belt is characterized by the seamless belt according to any one of claims 1 to 3.

  Invention of Claim 6 manufactures a seamless belt using the coating liquid containing a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and polyoxyethylene alkylphenyl ether modified silicone. The manufacturing method of the seamless belt is characterized.

  In the invention according to claim 7, a coating liquid containing a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone is applied to the support. A step of extending the coating, a step of removing the solvent in the coating applied and cast on the support by heating, a step of heating and promoting the imidation of the precursor contained in the coating, and formation And a step of releasing the applied coating film from the support.

  According to an eighth aspect of the present invention, there is provided an electrophotographic apparatus equipped with a belt constituting unit that transfers a toner developed image formed on an image carrier and forms an image on a recording medium. 3. An electrophotographic apparatus that is a seamless belt according to any one of 3).

  According to the ninth aspect of the present invention, a plurality of color toner developed images sequentially formed on the image carrier are sequentially superimposed on the intermediate transfer belt to perform primary transfer, and the primary transfer images are collectively recorded on a recording medium. An electrophotographic apparatus equipped with a belt component that is secondarily transferred to the belt is characterized in that the belt component is an electrophotographic apparatus that is a seamless belt according to any one of claims 1 to 3.

  The invention described in claim 10 is characterized by a coating liquid containing a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone.

  In a seamless belt formed using a coating liquid containing a filler and polyimide or polyamideimide, the coating liquid includes a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxy A seamless belt containing ethylene alkylphenyl ether-modified silicone prevents surface defects such as yuzu skin and turtle shell pattern, and evenly disperses inorganic fillers and is smooth and homogeneous with no residual air bubbles. A seamless belt excellent in heat resistance is provided. And because it has excellent surface uniformity and no defects such as bubbles, it is durable for electrophotographic drive members equipped in electrophotographic devices that are subject to severe mechanical and electrical hazards, that is, belt components. It can be used as an excellent member.

  By adjusting the content of polyoxyethylene alkylphenyl ether-modified silicone within the range of 0.005 to 1.0 wt% of the coating solution, the effect of preventing the formation of yuzu skin and tortoiseshell patterns during seamless belt formation As a result, the occurrence of a repelling phenomenon at the time of coating can be prevented, and the flow pattern of the liquid and the appearance of a wind pattern during drying by a hot air circulating dryer can be suppressed. Furthermore, the releasability from the mold is improved, and the seamless belt can be taken out without being damaged.

  In addition, by making the seamless belt have a film thickness of 50 μm or more, various performances required for the belt components equipped in the electrophotographic apparatus, for example, durability against mechanical and electrical repeated hazards, The physical dimension stability is satisfied and is preferable. Even in the case of a thick film of 50 μm or more, the coating liquid in the present invention can provide an excellent seamless belt as described in claims 1 and 2.

  Further, by applying the seamless belt of the present invention as a belt component to be equipped in a seamless belt electrophotographic apparatus for a belt component, and a belt structure to be equipped in a secondary transfer type electrophotographic apparatus By applying the seamless belt according to the present invention to a part, particularly an intermediate transfer belt, it is possible to improve durability against repeated mechanical and electrical severe hazards.

  In addition, with the seamless belt manufacturing method of the present invention, even in the case of thick films (50 μm or more), there are no surface defects such as yuzu skin and turtle shell pattern, the inorganic filler is uniformly dispersed, and there is no air bubbles. Seamless belts are provided.

In addition, the use of the seamless belt according to the present invention for the belt component equipped in the electrophotographic apparatus configuration improves durability and stabilizes high-quality images even during long-term image formation. Can be provided.
In addition, by using the coating liquid having the structure of the present invention, even when it is a thick film of 50 μm or more, there are no surface defects (such as a yuzu skin and a turtle shell pattern), and the dispersion of the inorganic filler is made uniform. In addition, it is possible to provide a smooth and uniform seamless belt with no bubbles remaining.

  Hereinafter, embodiments of the present invention will be described in detail. As described above, the seamless belt including the filler and the polyimide or polyamideimide in the present invention is formed by modifying the filler, the polyimide precursor or the polyamideimide precursor, the organic polar solvent, and the polyoxyethylene alkylphenyl ether modification. It is carried out using a coating solution containing silicone.

  Hereinafter, the coating liquid will be described. As described above, in the case of using a coating solution prepared by simply using a filler, a polyimide precursor or a polyamideimide precursor, and a solvent (for example, N-methylpyrrolidone), a thin film is formed (centrifugal molding). Etc.) Occasionally, the surface of the coating film becomes rough, such as a yuzu skin or a turtle shell pattern. This roughness adversely affects the dispersibility of the inorganic filler, resulting in non-uniform dispersion. In particular, when the inorganic filler is an electric resistance adjusting agent (referred to as a resistance adjusting agent for short), if the dispersion is non-uniform, the resistance value also becomes non-uniform, and for the belt constituent part equipped in the electrophotographic apparatus described later. Such a seamless belt, for example, a seamless belt that forms an image such as an intermediate transfer belt, causes an abnormal image.

  In addition, if a heating and heating process is performed to imidize the precursor while maintaining such a rough surface state, minute cracks are generated. When such micro cracks are formed, for example, when used for a drive member equipped in an electrophotographic apparatus, that is, a member for a belt component, it causes a belt crack in repeated use and lacks durability. Become.

  Furthermore, it is necessary to peel from the mold after the final firing step. Usually, the mold is subjected to a treatment that is easy to release, but the effect of the release layer may be reduced during repeated use at 250 ° C. or higher, making it difficult to release. Moreover, when meeting the request | requirement of high mechanical durability like the use of this invention, it is a material which is hard to release.

  Therefore, in the present invention, even in the case of forming a thick film (50 μm or more), surface roughness (surface roughness such as a yuzu skin or turtle shell pattern) does not occur, and the inorganic filler is uniformly dispersed. In order to suppress the generation of bubbles and prevent the formation of cracks, the problem can be solved by including polyoxyethylene alkylphenyl ether-modified silicone as a component of the coating liquid.

  The polyoxyethylene alkylphenyl ether-modified silicone is, for example, a compound represented by the following formula (1), and has an alkylphenyl group and a polyoxyethylene group, so that it is compatible with resins and polar organic solvents, pigments Excellent dispersibility. Moreover, high release property is shown by the effect of both an alkylphenyl group and dimethyl silicone. Furthermore, since the compatibility with the coating liquid is good, it can be contained in a large amount, and a sufficient release effect can be obtained.

  In addition, it further improves the prevention of the formation of yuzu skin and turtle shell patterns, and also prevents the occurrence of repellency during coating. Moreover, the expression of the flow pattern of the liquid at the time of coating and the wind pattern at the time of drying by a hot air circulation dryer can be suppressed. The polyoxyethylene alkylphenyl ether-modified silicone has cellularity, but a preferable one can be selected in terms of molecular weight and modification ratio. It can also be improved by using together with a defoaming siloxane compound such as dimethylsiloxane.

  Next, the filler contained as a component of the coating liquid of the present invention will be described. As the filler, various materials and forms are used as necessary in order to obtain desired characteristics according to the purpose. In addition, as mentioned above, a filler comprises a coating liquid in the state disperse | distributed to the organic polar solvent solution (containing the siloxane compound used for this invention) of a polyimide precursor or a polyamideimide precursor.

  Next, the filler contained as a component of the coating liquid of the present invention will be described. As fillers, reinforcing materials, lubricants, heat conduction materials, resistance control materials, etc. have desired characteristics according to the purpose, so that various materials and forms of inorganic and / or organic materials can be used as fillers as necessary. Although used, polyimide (polyamideimide) often uses an inorganic filler particularly during film formation. Moreover, what added the organic substance to the inorganic filler is also used. As described above, the filler constitutes the coating liquid in a state of being dispersed in an organic polar solvent solution of the polyimide precursor or polyamideimide precursor (containing the siloxane compound used in the present invention).

  When used as a seamless belt in the present invention, particularly as a seamless belt (electrophotographic seamless belt) for a belt component (driving unit) equipped in an electrophotographic apparatus, various components can be used depending on the application. However, an inorganic filler having a reinforcing effect as described above is indispensable from the viewpoint of mechanical strength.

  Examples of the electrophotographic seamless belt (electrophotographic seamless belt) used in the belt constituting unit provided in the electrophotographic apparatus include an intermediate transfer belt, a transfer conveyance belt, and a fixing belt. When used as a fixing belt, it is necessary to add an inorganic filler with high thermal conductivity. On the other hand, when used as a transfer conveying belt or an intermediate transfer belt, a resistance control agent for controlling electric resistance. Is necessary.

  As the resistance control agent, carbon black, graphite, or metal such as copper, tin, aluminum, indium, tin oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, tin oxide doped with antimony, Examples thereof include metal oxide fine powders such as indium oxide doped with tin. In addition, as an ion conductive resistance control agent, tetraalkylammonium salt, trialkylbenzyl, ammonium salt, alkylsulfonate, alkylbenzenesulfonate, alkylsulfate, glycerol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine Polyoxyethylene fatty alcohol ester, alkyl betaine, lithium perchlorate and the like may be used in combination. In addition, the resistance control agent in this invention is not limited to these exemplary compounds.

  Further, in the case of a coating liquid comprising the polyimide precursor or polyamideimide precursor of the present invention and an organic polar solvent such as N-methylpyrrolidone, carbon black is preferably used among the resistance control agents. It is done.

  In general, carbon black has high cohesion between particles and weak affinity with resin components and solvents, so it is very difficult to uniformly mix or disperse, and it is necessary to take some measures. For example, by reacting the surface functional group of carbon black with an organic compound having reactivity with the functional group, the affinity with the resin component and the solvent is increased, and it can be uniformly mixed or dispersed. It becomes like this.

  Examples of the organic compound include vinyl acetate, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-bromostyrene, p-chlorostyrene, and p-styrene. Styrene compounds such as sodium sulfonate, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate and other acrylate compounds, methyl methacrylate, methacryl Methacrylic acid ester compounds such as ethyl acetate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, N-substituted acrylates such as acrylonitrile, acrylamide, N-isopropylacrylamide, N-piperylacrylamide Riruamido compounds, divinyl benzene, methylene bisacrylamide, 1,3-butane diol but dimethacrylate crosslinking monomer, etc. and the like, but is not limited thereto.

  In addition, as a method for improving the dispersibility of carbon black, a method of treating carbon black with a coupling agent (for example, JP-A 63-175869, JP-A 63-158666, British Patent No. 1583564) (See British Patent No. 1583411). There is also a method of grafting a monomer component in the presence of carbon black (see, for example, JP-A No. 64-6965 and West German Patent No. 3102823). In the present invention, the treated carbon black obtained by one or two or more methods obtained by these known methods can be used alone or in admixture of two or more.

Next, the polyimide precursor or polyamideimide precursor which is the composition of the coating liquid in the present invention and the polyimide or polyamideimide produced by heat treatment (imidization) of the precursor will be described in detail.
Hereinafter, description will be made in the order of polyimide and polyamideimide.

Polyimide The polyimide used in the present invention is obtained via a polyamic acid (polyimide precursor) by a reaction of a generally known aromatic polycarboxylic acid anhydride or derivative thereof with an aromatic diamine. That is, polyimide is insoluble in solvents and the like due to its rigid main chain structure and has an infusible property. Therefore, a polyimide precursor that is soluble in an organic solvent from an acid anhydride and an aromatic diamine ( Polyamic acid or polyamic acid) is synthesized, and at this stage, molding is performed by various methods, and then the polyamic acid is subjected to dehydration reaction by heating or a chemical method to be cyclized (imidized) to obtain polyimide. The outline of the reaction is shown in the following chemical reaction formula (2).

In the formula, Ar ¹ represents a tetravalent aromatic residue containing at least one carbon 6-membered ring, and Ar ² represents a divalent aromatic residue containing at least one carbon 6-membered ring.

  Specific examples of the aromatic polyvalent carboxylic acid anhydride include, for example, ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4 ′. -Benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3 , 4-Dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxylphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2 , 3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7 , 8-phenanthrenetetracarboxylic dianhydride and the like. These may be used alone or in admixture of two or more.

  Next, specific examples of the aromatic diamine to be reacted with the aromatic polycarboxylic acid anhydride include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, and p-aminobenzyl. Amine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-amino Phenyl) sulfone, bis (4-aminophenyl) Luhon, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, Bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1- Bis [4- (4-aminophenoxy) phenyl] -ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3 3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (3- Aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] Ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4 -Aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′- [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4 -Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy] -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, and the like. These are used alone or in admixture of two or more.

  A polyimide precursor (polyamic acid) can be obtained by carrying out a polymerization reaction in an organic polar solvent using substantially equimolar amounts of the aromatic polycarboxylic anhydride component and the diamine component. Below, the manufacturing method of a polyamic acid is demonstrated concretely.

  Examples of the organic polar solvent used in the polymerization reaction of polyamic acid include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide and other acetamide solvents, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and other pyrrolidone solvents, phenol, o-, m-, or p- Phenolic solvents such as cresol, xylenol, halogenated phenol, catechol, ether solvents such as tetrahydrofuran, dioxane, dioxolane, alcohol solvents such as methanol, ethanol, butanol, cellosolve such as butyl cellosolve or hex Methyl phosphoramide, .gamma.-butyrolactone, etc. may be mentioned, it is desirable to use them alone or as a mixed solvent. The solvent is not particularly limited as long as it dissolves polyamic acid, but N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable.

  As an example for producing a polyimide precursor, first, one or a plurality of diamines are dissolved in the above organic solvent or diffused in a slurry state in an inert gas atmosphere such as argon or nitrogen. When at least one aromatic polycarboxylic acid anhydride or derivative thereof is added to this solution (either in a solid state, in a solution state dissolved in an organic solvent, or in a slurry state), it generates heat. A ring-opening polyaddition reaction occurs, and the viscosity of the solution rapidly increases, and a high molecular weight polyamic acid solution is obtained. The reaction temperature at this time is preferably controlled to −20 ° C. to 100 ° C., desirably 60 ° C. or less. The reaction time is about 30 minutes to 12 hours.

  The above is an example, and the addition procedure in the reaction is reversed. For example, an aromatic polyvalent carboxylic acid anhydride or derivative thereof is first dissolved or diffused in an organic solvent, and the diamine is added to this solution. May be. The diamine may be added in a solid state, in a solution state dissolved in an organic solvent, or in a slurry state. That is, the mixing order of the acid dianhydride component and the diamine component is not limited. Further, the aromatic tetracarboxylic dianhydride and the aromatic diamine may be simultaneously added to the organic polar solvent for reaction.

  As described above, the polyamic acid composition is dissolved in the organic polar solvent by polymerizing the aromatic polyvalent carboxylic acid anhydride or derivative thereof and the aromatic diamine component in about an equimolar amount of the organic polar solvent. A polyimide precursor solution is obtained in a uniformly dissolved state.

  As the polyimide precursor solution (polyamic acid solution) in the present invention, the one synthesized as described above can be used, but the so-called polyamic acid composition is simply dissolved in an organic solvent. What is marketed as a polyimide varnish can also be obtained and used.

  Examples of this include Trenys (manufactured by Toray Industries, Inc.), U-Varnish (manufactured by Ube Industries, Ltd.), Rika Coat (manufactured by Nippon Nippon Chemical Co., Ltd.), Optmer (manufactured by JSR), SE812 (manufactured by Nissan Chemical Industries), CRC8000 ( Sumitomo Bakelite Co., Ltd.).

  The filler is mixed and dispersed in the synthesized or obtained polyamic acid solution, and the siloxane compound (polydimethylsiloxane or alkylene oxide-modified polymethylsiloxane) according to the present invention is added and mixed to prepare a coating solution. The coating liquid is applied to a support (molding mold) as described later, and then subjected to a treatment such as heating, whereby conversion (imidation) from polyamic acid, which is a polyimide precursor, to polyimide is performed.

  That is, the polyamic acid can be imidized by a heating method or a chemical method. The heating method is a method of converting polyamic acid to polyimide by heat treatment at 200 to 350 ° C., and is a simple and practical method for obtaining polyimide (polyimide resin).

  On the other hand, the chemical method is a method in which polyamic acid is reacted with a dehydrating cyclization reagent (such as a mixture of carboxylic acid anhydride and tertiary amine), and then heat-treated to completely imidize, which is compared with the heating method. Since the method is complicated and costly, a heating method is usually used. In order to exhibit the intrinsic performance of polyimide, it is necessary to complete imidization by heating to a temperature above the glass transition temperature of the corresponding polyimide.

The progress of imidization (degree of imidization) can be evaluated by a commonly performed method for measuring the imidization rate.
As a method for measuring such an imidization rate, for example, nuclear magnetic resonance spectroscopy calculated from an integration ratio of 1H attributed to an amide group in the vicinity of 9 to 11 ppm and 1H attributed to an aromatic ring in the vicinity of 6 to 9 ppm. Various methods such as the NMR method, the Fourier transform infrared spectroscopy (FT-IR method), the method for quantifying moisture accompanying imide ring closure, and the carboxylic acid neutralization titration method are used. -Lier transformation infrared spectroscopy (FT-IR method) is the most common method.

In the Fourier transform infrared spectroscopy (FT-IR method), the imidization rate is defined as follows from the change in the characteristic absorption band, for example. That is, assuming that (A) is the number of moles of imide groups at the firing stage (imidation treatment stage) and (B) is the number of moles of imide groups when 100% imidized (theoretical), Is done.
Imidation rate = [(A)] / (B)]] × 100
The number of moles of the imide group in this definition can be determined from the absorbance ratio of the characteristic absorption of the imide group measured by the FT-IR method. For example, as a typical characteristic absorption, the imidization ratio can be evaluated using the following absorbance ratio.

(1) Absorbance ratio between 725 cm ⁻¹ (an imide ring C═O group bending vibration band) which is one of the characteristic absorptions of imide and the characteristic absorption of benzene ring of 1,015 cm ⁻¹ .
(2) Absorbance ratio between 1,380 cm ⁻¹ (inflection band of imide ring C—N group), which is one of characteristic absorptions of imide, and 1,500 cm ⁻¹ of characteristic absorption of benzene rings.
(3) Absorbance ratio between 1,720 cm ⁻¹ (immobilization band of imide ring C═O group) which is one of characteristic absorptions of imide and 1,500 cm ⁻¹ of characteristic absorption of benzene ring.
(4) 1,720 cm ⁻¹ , which is one of the characteristic absorptions of imide, and 1,670 cm ⁻¹ (interaction between amide group N—H bending vibration and C—N stretching vibration) Absorbance ratio.
In addition, if it is confirmed that the amide group-derived multiple absorption band from 3000 to 3300 cm ⁻¹ has disappeared, the reliability of imidization completion is further increased.

Next, polyamideimide will be described.
Polyamideimide Polyamideimide is a resin having a rigid imide group and an amide group imparting flexibility in the molecular skeleton, and a polyamideimide having a generally known structure is used as the polyamideimide used in the present invention. be able to.
Generally, as a method for synthesizing a polyamideimide resin, an acid chloride method (a): a derivative halide of a trivalent carboxylic acid having an acid anhydride group, most typically a chloride compound of the derivative and a diamine are used as solvents. A known method for producing it by reacting in it is known (for example, see Japanese Examined Patent Publication No. 42-15637). Alternatively, as another method, an isocyanate method (b): a known method for producing a trivalent derivative containing an acid anhydride group and a carboxylic acid and an aromatic isocyanate in a solvent (for example, Japanese Examined Patent Publication No. 44-19274). No.) are known, and any of them can be used. Each manufacturing method will be described below.

(A) Acid chloride method As a derivative halide compound of a trivalent carboxylic acid having an acid anhydride group, for example, compounds represented by the following general formula (3) and general formula (4) can be used.

  In the above formula (3), X represents a halogen element.

In the above formula (4), X represents a halogen element, and Y is a divalent group, for example, one selected from —CH ₂ —, —CO—, —SO ₂ — or —O— or 2 or more.

  In each of the above formulas, the halogen element is preferably chloride, and specific examples of derivatives include terephthalic acid, isophthalic acid, 4, 4 ′ biphenyl dicarboxylic acid, 4, 4 ′ biphenyl ether dicarboxylic acid, 4, 4 ′ biphenyl sulfone dicarboxylic acid. Acid, 4, 4 'benzophenone dicarboxylic acid, pyromellitic acid, trimellitic acid, 3, 3', 4, 4 'benzophenone tetracarboxylic acid, 3, 3,' 4, 4 'biphenylsulfone tetracarboxylic acid, 3, Polyvalent carboxylic acids such as 3 ′, 4 and 4 ′ biphenyltetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, and 1,2 cyclohexanedicarboxylic acid Of acid chloride.

  On the other hand, the diamine is not particularly limited, and any of aromatic diamine, aliphatic diamine, and alicyclic diamine can be used, and aromatic diamine is preferably used. Aromatic diamines include m-phenylenediamine, p-phenylenediamine, oxydianiline, methylenediamine, hexafluoroisopropylidenediamine, diamino-m-xylylene, diamino-p-xylylene, 1,4-naphthalenediamine, 1, 5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2′-bis- (4-aminophenyl) propane, 2,2′-bis- (4-aminophenyl) hexafluoro Propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ether, 3,4-diaminobiphenyl, 4,4'-diaminobenzophenone 3,4-diaminodiphenyl ether Ter, isopropylidenedianiline, 3,3′-diaminobenzophenone, o-tolidine, 2,4-tolylenediamine, 1,3-bis- (3-aminophenoxy) benzene, 1,4-bis- (4- Aminophenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 2,2-bis- [4- (4-aminophenoxy) phenyl] propane, bis- [4- (4-aminophenoxy) phenyl ] Sulfone, bis- [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis- (4-aminophenoxy) biphenyl, 2,2′-bis- [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide and the like.

  Also, siloxane compounds having amino groups at both ends as diamines, such as 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (3-amino Propyl) polydimethylsiloxane, 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (3-aminophenoxymethyl) polydimethylsiloxane, 1, 3, -bis (2- (3-aminophenoxy) ethyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (2- (3-aminophenoxy) ethyl) polydimethylsiloxane, , 3-bis (3- (3-aminophenoxy) propyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (3- (3-aminophenoxy) propi E) If polydimethylsiloxane or the like is used, a silicone-modified polyamideimide can be obtained.

  In order to obtain the polyamideimide (polyamideimide resin) in the present invention by the acid chloride method, the above-described trivalent carboxylic acid derivative halide and diamine having an acid anhydride group are used in the same manner as in the production of the polyimide resin. After dissolving in an organic polar solvent, it is reacted at a low temperature (0 to 30 ° C.) to obtain a polyamideimide precursor (polyamide-amic acid).

  The organic polar solvent that can be used is the same as that of the polyimide, and a formamide solvent (for example, a sulfoxide solvent such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, etc.), Acetamide solvents (eg, N, N-dimethylacetamide, N, N-diethylacetamide, etc.), pyrrolidone solvents (eg, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, etc.), phenol solvents ( For example, phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, etc.), ether solvent (eg, tetrahydrofuran, dioxane, dioxolane, etc.), alcohol solvent (eg, methanol, ethanol, butanol) etc , Cellosolve type solvents (e.g., butyl cellosolve, etc.), or hexamethylphosphoramide, γ- butyrolactone. These are preferably used alone or as a mixed solvent, and are not particularly limited as long as they dissolve polyamic acid. Particularly preferably used solvents are N, N-dimethylacetamide and N-methyl-2-pyrrolidone.

  The polyamide / polyamic acid solution obtained above is mixed with the filler and the siloxane compound (polydimethylsiloxane or alkylene oxide-modified polymethylsiloxane) of the present invention to prepare a coating solution. After the coating liquid is applied to the support (molding die), the polyamic acid is converted to polyimide (imidation) by treatment such as heating.

  Examples of the imidization method include a method of dehydrating and ring-closing by heat treatment, and a method of chemically ring-closing using a dehydrating and ring-closing catalyst. When dehydrating and ring-closing by heat treatment, for example, the reaction temperature is 150 to 400 ° C., preferably 180 to 350 ° C., and the heat treatment time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. When a dehydration ring closure catalyst is used, the reaction temperature is 0 to 180 ° C., preferably 10 to 80 ° C., and the reaction time is several tens of minutes to several days, preferably 2 to 12 hours. Examples of the dehydration ring closure catalyst include acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid.

As the derivative of the trivalent carboxylic acid having an acid anhydride group used in the isocyanate method, for example, a compound represented by the following general formula (5) or the following general formula (6) can be used.

  In formula (5), R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.

In formula (6), R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and Y represents —CH ₂ —, —CO—, —SO ₂ —, or —O—.
Any derivative having the above general formula can be used, but the most typical example is trimellitic anhydride. These trivalent carboxylic acid derivatives having an acid anhydride group can be used alone or in combination depending on the purpose.

  Next, as one aromatic polyisocyanate used for the synthesis of the polyamideimide of the present invention, for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenyl ether diisocyanate, 4, 4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3,3'-diisocyanate, biphenyl-3,4'-diisocyanate, 3,3' -Dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4 , 4'-Diisocyanate 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate and the like. .

  These aromatic polyisocyanates can be used alone or in combination. Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diene as necessary. Aliphatic such as isocyanate and lysine diisocyanate, alicyclic isocyanate and trifunctional or higher polyisocyanate can also be used.

  In the solution containing the polyamideimide precursor obtained by adjusting the above-mentioned trivalent carboxylic acid derivative having an acid anhydride group and an aromatic polyisocyanate in an organic polar solvent, the filler, and A coating solution is prepared by mixing with a siloxane compound (polydimethylsiloxane or alkylene oxide-modified polymethylsiloxane). After the coating liquid is applied to the support, the polyamideimide precursor is converted to polyamideimide by heat treatment. Upon conversion to polyamideimide by this method, polyamideimide is generated without generating a carbonic acid (generally generating carbon dioxide). The following chemical reaction formula (7) shows an example of the reaction of polyamide imidization when trimellitic anhydride and aromatic isocyanate are used.

In the formula (7), Ar represents a divalent aromatic group.
The polyimide and polyamideimide shown above are usually used alone, but those selected in consideration of compatibility can also be used in combination.
Moreover, the copolymer which has a polyimide repeating unit and a polyamideimide repeating unit may be sufficient.

Next, a method for producing a seamless belt using the coating liquid containing the polyimide precursor or the polyamideimide precursor will be described.
That is, in the present invention, a filler, a polyimide precursor or a polyamideimide precursor, N-methylpyrrolidone, a polydimethylsiloxane having a kinematic viscosity at 25 ° C. of 1 cSt or more and 20 cSt or less, or 30 cSt or more and 100 cSt or less. When a seamless belt is produced using a coating liquid containing a certain alkylene oxide-modified polyoxyethylene alkylphenyl ether-modified silicone, it can be achieved by including the following steps. That is, a step (1) of applying and casting the coating liquid on a support (molding mold), a step of removing the solvent in the coating film applied and cast on the support by heating (2), It can be manufactured by the step (3) for promoting imidation of the precursor contained in the coating film by heating at elevated temperature, and the step (4) for releasing the formed thin film from the support to form a seamless belt. .

  First, a case where centrifugal molding is used as a support (molding mold) will be described as an example. The following description is an example and the conditions are not limited thereto. Centrifugal molding is composed of a cylindrical rotating body. While this cylindrical rotating body is slowly rotated, coating and casting (coating film coating) is performed so that the coating liquid is uniform over the entire inner surface of the cylinder. Form. Thereafter, the rotation speed is increased to a predetermined speed, and when the predetermined speed is reached, the rotation speed is maintained at a constant speed and rotation is continued for a desired time. And the solvent in a coating film is evaporated at the temperature of about 80-150 degreeC, heating up gradually while rotating. In this process, it is preferable to efficiently circulate and remove atmospheric vapor (such as a volatilized solvent). When a self-supporting film is obtained, it is returned to room temperature, transferred to a heating furnace (firing furnace) capable of high-temperature treatment, heated in steps, and finally heated at about 250 ° C. to 450 ° C. ( Calcination), and sufficiently imidization or polyamide-imidization of the polyimide precursor or polyamide-imide precursor is performed. After completion of imidization and the like, the thin film is peeled off from the mold by slow cooling. A seamless belt is thus formed. In addition, it is preferable to previously form a mold release agent or a mold release layer on the mold so that the mold can be easily peeled off.

  Next, the seamless belt used in the belt constituting unit equipped in the electrophotographic apparatus according to the present invention will be described in detail below with reference to a schematic diagram of relevant parts. The schematic diagram is an example, and the present invention is not limited to this.

  The schematic diagram of FIG. 1 shows a schematic configuration of the main part of an electrophotographic apparatus equipped with a belt component and the like. An intermediate transfer unit 500 that is a belt component shown in FIG. 1 includes an intermediate transfer belt 501 that is an intermediate transfer member stretched around a plurality of rollers. Around the intermediate transfer belt 501, a secondary transfer bias roller 605 that is a secondary transfer charge applying unit of the secondary transfer unit 600, a belt cleaning blade 504 that is an intermediate transfer member cleaning unit, and a lubricant for a lubricant application unit. A lubricant application brush 505 or the like that is an application member is disposed so as to face each other.

  A position detection mark (not shown) is provided on the outer peripheral surface or the inner peripheral surface of the intermediate transfer belt 501. However, on the outer peripheral surface side of the intermediate transfer belt 501, it is necessary to devise a position detection mark that avoids the passing area of the belt cleaning blade 504, which may be difficult to arrange. A position detection mark may be provided on the inner peripheral surface side of the intermediate transfer belt 501. An optical sensor 514 serving as a mark detection sensor is provided at a position between the primary transfer bias roller 507 and the belt driving roller 508 where the intermediate transfer belt 501 is bridged.

  The intermediate transfer belt 501 includes a primary transfer bias roller 507 serving as a primary transfer charge applying unit, a belt driving roller 508, a belt tension roller 509, a secondary transfer counter roller 510, a cleaning counter roller 511, and a feedback current detection roller 512. It is stretched around. Each roller is formed of a conductive material, and each roller other than the primary transfer bias roller 507 is grounded. The primary transfer bias roller 507 is applied with a transfer bias controlled to a predetermined current or voltage according to the number of superimposed toner images by a primary transfer power source 801 controlled at a constant current or voltage. ing.

  The intermediate transfer belt 501 is driven in the arrow direction by a belt driving roller 508 that is driven to rotate in the arrow direction by a drive motor (not shown). The intermediate transfer belt 501 as a belt component is usually a semiconductor or an insulator and has a single-layer or multi-layer structure, but the seamless belt of the present invention is preferably used, thereby improving durability. Excellent image formation can be realized. Further, the intermediate transfer belt is set to be larger than the maximum sheet passing size in order to superimpose the toner images formed on the photosensitive drum 200.

  A secondary transfer bias roller 605 serving as a secondary transfer unit is attached to and separated from a belt outer peripheral surface of the intermediate transfer belt 501 in a portion stretched around the secondary transfer counter roller 510 by a contact / separation mechanism, which will be described later. It is configured to be able to contact and separate. The secondary transfer bias roller 605 is disposed so as to sandwich the transfer paper P, which is a recording medium, between the portion of the intermediate transfer belt 501 stretched around the secondary transfer counter roller 510 and a constant current. A transfer bias having a predetermined current is applied by a secondary transfer power source 802 to be controlled.

  The registration roller 610 feeds the transfer sheet P, which is a transfer material, between the secondary transfer bias roller 605 and the intermediate transfer belt 501 stretched around the secondary transfer counter roller 510 at a predetermined timing. The secondary transfer bias roller 605 is in contact with a cleaning blade 608 as a cleaning unit. The cleaning blade 608 is for removing the adhering matter adhering to the surface of the secondary transfer bias roller 605 for cleaning.

  In the color copying machine having such a configuration, when an image forming cycle is started, the photosensitive drum 200 is rotated in a counterclockwise direction indicated by an arrow by a drive motor (not shown), and Bk ( Black) toner image formation, C (cyan) toner image formation, M (magenta) toner image formation, and Y (yellow) toner image formation are performed. The intermediate transfer belt 501 is rotated clockwise by the belt driving roller 508 as indicated by an arrow. As the intermediate transfer belt 501 rotates, the primary transfer of the Bk toner image, the C toner image, the M toner image, and the Y toner image is performed by the transfer bias by the voltage applied to the primary transfer bias roller 507. Finally, toner images are formed on the intermediate transfer belt 501 in the order of Bk, C, M, and Y.

  For example, the Bk toner image formation is performed as follows. In FIG. 1, a charging charger 203 uniformly charges the surface of the photosensitive drum 200 to a predetermined potential with a negative charge by corona discharge. The timing is determined based on the belt mark detection signal, and raster exposure with laser light is performed based on the Bk color image signal by a writing optical unit (not shown). When this raster image is exposed, the charge proportional to the exposure light amount disappears in the exposed portion of the surface of the photosensitive drum 200 that is initially uniformly charged, and a Bk electrostatic latent image is formed. When the negatively charged Bk toner on the developing roller of the Bk developing device 231K comes into contact with this Bk electrostatic latent image, the toner does not adhere to the remaining portion of the photosensitive drum 200, and the charge is not charged. The toner is attracted to the nonexposed portion, that is, the exposed portion, and a Bk toner image similar to the electrostatic latent image is formed.

  The Bk toner image formed on the photosensitive drum 200 in this manner is primarily transferred onto the belt outer peripheral surface of the intermediate transfer belt 501 that is rotating at a constant speed while being in contact with the photosensitive drum 200. Some untransferred residual toner remaining on the surface of the photoreceptor drum 200 after the primary transfer is cleaned by the photoreceptor cleaning device 201 in preparation for reuse of the photoreceptor drum 200. On the photosensitive drum 200 side, the process proceeds to the Y image forming process after the Bk image forming process, and reading of the Y image data by the color scanner starts at a predetermined timing, and the photosensitive drum is written by laser beam writing with the Y image data. A Y electrostatic latent image is formed on the surface of 200.

  Then, after the rear end portion of the previous Bk electrostatic latent image passes and before the front end portion of the T electrostatic latent image reaches, the revolver developing unit 230 is rotated, and the Y developing device 231Y develops. The Y electrostatic latent image is developed with Y toner. Thereafter, the development of the Y electrostatic latent image area is continued. When the trailing edge of the Y electrostatic latent image passes, the revolver developing unit is rotated in the same manner as in the case of the previous Bk developing machine 231K, and the next The C developing machine 231C is moved to the developing position. This is also completed before the leading edge of the next C electrostatic latent image reaches the developing position. Note that the C and M image forming steps are the same as the Bk and Y steps described above because the color image data reading, electrostatic latent image forming, and developing operations are the same as those described above.

  The Bk, Y, C, and M toner images sequentially formed on the photosensitive drum 200 in this way are sequentially aligned on the same surface on the intermediate transfer belt 501 and primarily transferred. As a result, a toner image having a maximum of four colors superimposed on the intermediate transfer belt 501 is formed. On the other hand, at the time when the image forming operation is started, the transfer paper P is fed from a paper feed unit such as a transfer paper cassette or a manual feed tray, and is waiting at the nip of the registration roller 610.

  When the leading edge of the toner image on the intermediate transfer belt 501 reaches the secondary transfer portion where the nip is formed by the intermediate transfer belt 501 stretched around the secondary transfer counter roller 510 and the secondary transfer bias roller 605. Then, the registration roller 610 is driven so that the leading edge of the transfer paper P coincides with the leading edge of the toner image, and the transfer paper P is conveyed along the transfer paper guide plate 601, and the transfer paper P and the toner image are transferred. Resist alignment is performed.

  In this way, when the transfer paper P passes through the secondary transfer portion, the four-color superimposed toner image on the intermediate transfer belt 501 is transferred by the transfer bias applied by the secondary transfer power source 802 to the secondary transfer bias roller 605. Are collectively transferred (secondary transfer) onto the transfer paper P. After the transfer paper P is conveyed along the transfer paper guide plate 601 and passed through a portion facing the transfer paper neutralization charger 606 composed of a static elimination needle disposed on the downstream side of the secondary transfer portion, the transfer paper P is discharged. Then, it is sent toward the fixing device 270 by the belt conveying device 210 which is a belt component (see FIG. 1). Then, after the toner image is melted and fixed at the nip portions of the fixing rollers 271 and 272 of the fixing device 270, the transfer paper P is sent out of the apparatus main body by a discharge roller (not shown), and is stacked face up on a copy tray (not shown). Is done. Note that the fixing device 270 may be configured to include a belt component if necessary.

  On the other hand, the surface of the photosensitive drum 200 after the belt transfer is cleaned by the photosensitive member cleaning device 201 and is uniformly discharged by the discharging lamp 202. Further, residual toner remaining on the outer peripheral surface of the intermediate transfer belt 501 after the toner image is secondarily transferred to the transfer paper P is cleaned by the belt cleaning blade 504. The belt cleaning blade 504 is configured to be brought into contact with and separated from the belt outer peripheral surface of the intermediate transfer belt 501 at a predetermined timing by a cleaning member separating and contacting mechanism (not shown).

  A toner seal member 503 that contacts and separates from the belt outer peripheral surface of the intermediate transfer belt 501 is provided on the upstream side of the belt cleaning blade 504 in the movement direction of the intermediate transfer belt 501. The toner seal member 503 receives the falling toner dropped from the belt cleaning blade 504 when cleaning the residual toner, and prevents the falling toner from scattering on the transfer path of the transfer paper P. The toner seal member 503 is brought into contact with and separated from the belt outer peripheral surface of the intermediate transfer belt 501 together with the belt cleaning blade 504 by the cleaning member separating and contacting mechanism.

  The lubricant 506 scraped by the lubricant application brush 505 is applied to the outer peripheral surface of the intermediate transfer belt 501 from which the residual toner has been removed in this way. The lubricant 506 is made of, for example, a solid body such as zinc stearate, and is disposed so as to come into contact with the lubricant application brush 505. Further, residual charges remaining on the outer peripheral surface of the intermediate transfer belt 501 are removed by a neutralizing bias applied by a belt neutralizing brush (not shown) that is in contact with the outer peripheral surface of the intermediate transfer belt 501. Here, the lubricant application brush 505 and the belt neutralizing brush are brought into contact with and separated from the belt outer peripheral surface of the intermediate transfer belt 501 at a predetermined timing by respective contact and separation mechanisms (not shown). .

  Here, at the time of repeat copy, the operation of the color scanner and the image formation on the photosensitive drum 200 are performed at a predetermined timing following the first color (M) image formation process of the first sheet and the first color of the second sheet. The process proceeds to the image forming process (Bk). Further, the intermediate transfer belt 501 has a second Bk toner in the area cleaned by the belt cleaning blade 504 on the outer peripheral surface of the belt following the batch transfer process of the first four-color superimposed toner image to the transfer paper. The image is first transferred. After that, the operation is the same as the first sheet. The above is a copy mode for obtaining a four-color full-color copy. In the three-color copy mode and the two-color copy mode, the same operation as described above is performed for the designated color and the number of times. In the case of the single color copy mode, only the predetermined color developing machine of the revolver developing unit 230 is set in the developing operation state until the predetermined number of sheets is completed, and the belt cleaning blade 504 is kept in contact with the intermediate transfer belt 501. The copy operation is performed in the state.

  In the above-described embodiment, the copying machine including only one photosensitive drum 1 has been described. However, the present invention may be configured such that, for example, a plurality of photosensitive drums as illustrated in FIG. 2 are arranged in parallel along one intermediate transfer belt. The present invention can also be applied to the image forming apparatus.

  FIG. 2 shows a configuration of a four-drum digital color printer including four photosensitive drums 921BK, 921Y, 921M, and 921C for forming toner images of four different colors (black, yellow, magenta, and cyan). An example is shown.

  In FIG. 2, the printer main body 910 includes an image writing unit 912, an image forming unit 913, and a paper feeding unit 914 for performing color image formation by electrophotography. Based on the image signal, the image processing unit performs image processing to convert the signal into black (BK), magenta (M), yellow (Y), and cyan (C) color signals for image formation, and transmits the signals to the image writing unit 912. To do. The image writing unit 912 is a laser scanning optical system including, for example, a laser light source, a deflector such as a rotary polygon mirror, a scanning imaging optical system, and a mirror group. An image writing unit (photosensitive body) 921BK, 921M, 921Y, and 921C that has a writing optical path and is provided for each color of the image forming unit 913 performs image writing corresponding to each color signal.

  The image forming unit 913 includes photoconductors 921BK, 921M, 921Y, and 921C that are image carriers for black (BK), magenta (M), yellow (Y), and cyan (C). As each photoconductor for each color, an OPC photoconductor is usually used. Around each of the photosensitive members 921BK, 921M, 921Y, and 921C, there are a charging device, a laser beam exposure unit from the writing unit 912, and developing devices 920BK, 920M, 920Y, black, magenta, yellow, and cyan. 920C, primary transfer bias rollers 923BK, 923M, 923Y, and 923C as primary transfer units, a cleaning device (not shown), and a photosensitive member discharging device (not shown) are arranged. The developing devices 920BK, 920M, 920Y, and 920C employ a two-component magnetic brush developing system. The intermediate transfer belt 922, which is a belt component, is interposed between the respective photosensitive members 921BK, 921M, 921Y, and 921C and the respective primary transfer bias rollers 923BK, 923M, 923Y, and 923C, and is formed on the respective photosensitive members. The toner images of each color are sequentially superimposed and transferred.

  On the other hand, the transfer paper P is fed from the paper feed unit 914 and then is carried by the transfer conveyance belt 950 which is a belt component through the registration roller 916. When the intermediate transfer belt 922 and the transfer conveyance belt 950 come into contact, the toner image transferred onto the intermediate transfer belt 922 is subjected to secondary transfer (collective transfer) by a secondary transfer bias roller 960 as a secondary transfer unit. ) As a result, a color image is formed on the transfer paper P. The transfer paper P on which the color image is formed is conveyed to the fixing device 915 by the transfer conveying belt 950, and after the image transferred by the fixing device 915 is fixed, it is discharged out of the printer main body.

  The residual toner that is not transferred during the secondary transfer and remains on the intermediate transfer belt 922 is removed from the intermediate transfer belt 922 by the belt cleaning device 925. A lubricant application device (not shown) is disposed on the downstream side of the belt cleaning device 925. This lubricant application device includes a solid lubricant and a conductive brush that rubs against the intermediate transfer belt 922 to apply the solid lubricant. The conductive brush is always in contact with the intermediate transfer belt 922 and applies a solid lubricant to the intermediate transfer belt 922. The solid lubricant has an effect of improving the cleaning property of the intermediate transfer belt 922, preventing the occurrence of filming and improving the durability.

  The seamless belt according to the present invention can be suitably applied to an intermediate transfer belt type image forming apparatus equipped with the intermediate transfer belt 501 or 922 as described above, and a transfer conveyance belt instead of the intermediate transfer belt 501 or 922. The present invention can also be applied to a transfer / conveying belt type image forming apparatus equipped with the above. Further, in the case of an image forming apparatus using a transfer / conveying belt system, the present invention can be applied to either the 1-photosensitive drum system or the 4-photosensitive drum system.

[Example 1]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples without departing from the gist thereof.

[Example 2]
Preparation of coating liquid First, each equimolar amount of biphenyl-3,4,3 ′, 4′-tetracarboxylic anhydride and 4,4′-diaminodiphenyl ether was polymerized at room temperature in N-methylpyrrolidone solvent. To obtain a polyamic acid solution. This solution was prepared by mixing a carbon black (BP-L manufactured by Cabot) dispersion finely pulverized and dispersed in N-methylpyrrolidone with a bead mill.
The obtained carbon black-dispersed polyamic acid solution had a polyamic acid solid content of 13 wt%, carbon black of 3 wt%, and N-methylpyrrolidone of 84 wt%.
Furthermore, 0.01 wt% of polyoxyethylene alkylphenyl ether-modified silicone (FZ2133; manufactured by Nihon Unicar Co., Ltd.) was added to the carbon black-dispersed polyamic acid solution, and the mixture was stirred well to prepare a coating solution.

Production of Seamless Belt Next, a metal cylinder having an inner diameter of 100 mm and a length of 300 mm having a mirror finish is used as a mold, and the coating liquid is applied to the inner surface of the cylinder while rotating the cylinder at 50 rpm (times / minute). The solution was applied so as to be cast uniformly. When the coating has spread evenly after the predetermined total amount has been flowed, the number of revolutions is increased to 100 rpm, the hot air circulating dryer is introduced, the temperature is gradually raised to 120 ° C., and this temperature is maintained for 30 minutes for heating. did. Thereafter, the rotation was stopped, and the mixture was put into a heating furnace (firing furnace) capable of high temperature treatment, heated to 350 ° C., and maintained at this temperature for 30 minutes for heat treatment (firing).
After stopping the heating by treating for a predetermined time, the mold was taken out after gradually cooling to room temperature, and the formed coating film was peeled off from the inner surface of the cylinder to obtain a seamless belt having a film thickness of 90 μm.

Evaluation of Inner Surface Properties of Seamless Belt The surface state of the inner surface of the manufactured seamless belt was observed with a microscope (VH-8000 manufactured by Keyence).

Uniformity evaluation of surface resistance The surface resistance values of the inner surface and the outer surface of the seamless belt were measured at 10 points each and evaluated by the logarithmic difference between the maximum value and the minimum value. If the difference is 0.5 or less, it can be said that it is good.
The measuring device was a value 10 seconds after application of 500 V by Hiresta (Mitsubishi Chemical).

Evaluation of peelability from mold The peelability when peeling the seamless belt from the mold was evaluated.

[Examples 3 to 4]
It was the same except that the addition amount of the polyoxyethylene alkylphenyl ether-modified silicone in Example 1 was 0.005 wt%, 0.10 wt%, and 1.00 wt%.

[Comparative Examples 1-2]
It was the same except that the amount of polyoxyethylene alkylphenyl ether-modified silicone added to the coating solution in Example 1 was 0 wt% and 2.00 wt%.

[Example 5]
Preparation of coating solution First, an equimolar amount of trimellitic anhydride and 4,4′-diphenylmethane diisocyanate was polymerized at 150 ° C. in an N-methylpyrrolidone solvent to obtain a polyamideimide solution. This solution was prepared by mixing a carbon black (BP-L manufactured by Cabot) dispersion finely pulverized and dispersed in N-methylpyrrolidone with a bead mill. The obtained carbon black-dispersed polyamideimide solution had a polyamideimide solid content of 15 wt%, carbon black of 7 wt%, and N-methylpyrrolidone of 78 wt%.

  Further, 0.1 wt% of polyoxyethylene alkylphenyl ether-modified silicone (FZ2138; manufactured by Nihon Unicar Co., Ltd.) was added to the carbon black-dispersed polyamideimide solution, and the mixture was stirred well to prepare a coating solution.

Fabrication of seamless belt Next, as in Example 1, a metal cylinder having an inner diameter of 100 mm and a length of 300 mm having a mirror finish was used as a mold, and this cylinder mold was rotated at 50 rpm (times / minute) while applying the above coating. The working liquid was applied to the inner surface of the cylinder so as to be cast uniformly. When the coating has spread evenly after the entire amount has been flowed, the number of revolutions is increased to 100 rpm, the hot air circulating dryer is introduced, and the temperature is gradually raised to 120 ° C. and heated for 30 minutes while maintaining this temperature. did. Thereafter, the rotation was stopped, and the mixture was put into a heating furnace (baking furnace) capable of high temperature treatment, heated to 250 ° C., and heated (baked) while maintaining this temperature for 30 minutes.
After stopping the heating by treating for a predetermined time, the mold was taken out after gradually cooling to room temperature, and the formed coating film was peeled off from the inner surface of the cylinder to obtain a seamless belt having a film thickness of 85 μm.

[Comparative Example 3]
It was the same except that the polyoxyethylene alkylphenyl ether-modified silicone added to the coating solution in Example 5 was not added.
The results are shown in Table 1.

  From the above results, by adopting the constitution of the present invention, a belt having good properties can be obtained, and a durable, high-quality, highly stable seamless belt can be provided even when used for an electrophotographic member. Moreover, it can be easily peeled off from the mold, and highly efficient production becomes possible.

It is a principal part schematic diagram of the electrophotographic apparatus which uses the seamless belt of this invention. It is a schematic diagram of an electrophotographic apparatus for using the seamless belt of the present invention.

Explanation of symbols

P transfer paper 200 photoconductor drum 201 photoconductor cleaning device 202 static elimination lamp 203 charging charger 210 belt conveying device 230 revolver developing unit 231Y Y developing machine 231K Bk developing machine 231C C developing machine 231M M developing machine 270 fixing device 271, 272 fixing roller 500 Intermediate transfer unit 501 Intermediate transfer belt 503 Toner seal member 504 Belt cleaning blade 505 Lubricant application brush 507 Primary transfer bias roller 508 Belt drive roller 509 Belt tension controller 510 Secondary transfer counter roller 600 Secondary transfer unit 605 Secondary transfer Bias roller 606 Transfer paper static elimination charger 608 Cleaning blade 610 Registration roller 802 Secondary transfer power source 910 Printer main body 91 2 Image writing unit 913 Image forming unit 914 Paper feeding unit 915 Fixing device 916 Registration roller 920BK, 920M, 920Y, 920C Developing device 921BK, 921M, 921Y, 921C Photoconductor 922 Intermediate transfer belt 923BK, 923M, 923Y, 923C Primary Transfer bias roller 925 Belt cleaning device 950 Transfer conveyance belt 960 Secondary transfer bias roller

Claims (10)

In a seamless belt obtained using a coating liquid containing a filler and polyimide or polyamideimide,
The seamless belt, wherein the coating liquid contains a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and polyoxyethylene alkylphenyl ether-modified silicone.   The seamless belt according to claim 1, wherein the content of the polyoxyethylene alkylphenyl ether-modified silicone is 0.005 to 1.0 wt% of the coating solution.   The seamless belt according to claim 1 or 2, wherein the seamless belt has a film thickness of 50 µm or more. In a seamless belt for a belt constituent part equipped in an electrophotographic apparatus for transferring a toner developed image formed on an image carrier and forming an image on a recording medium,
The belt is a seamless belt according to any one of claims 1 to 3, and a seamless belt for a belt component. An electrophotographic apparatus for performing primary transfer by sequentially superimposing a plurality of color toner developed images sequentially formed on an image carrier on an intermediate transfer belt, and performing secondary transfer of the primary transfer image collectively to a recording medium In the seamless belt for the belt component equipped,
The said belt is the seamless belt in any one of Claims 1-3, The seamless belt for belt structure parts characterized by the above-mentioned.   A seamless belt comprising a coating liquid containing a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone. Production method. Applying and casting a coating liquid containing a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone on a support;
Removing the solvent in the coating film applied and cast on the support by heating;
A step of heating and heating to promote imidation of the precursor contained in the coating film,
And a step of releasing the formed coating film from the support. In an electrophotographic apparatus equipped with a belt component that transfers a toner developed image formed on an image carrier and forms an image on a recording medium.
An electrophotographic apparatus using the seamless belt according to claim 1 as the belt. A belt component that sequentially superimposes a plurality of color toner developed images sequentially formed on an image carrier on an intermediate transfer belt to perform primary transfer, and collectively transfers the primary transfer image to a recording medium. In an electrophotographic apparatus equipped with
The electrophotographic apparatus according to claim 1, wherein the belt component is the seamless belt according to claim 1.   A coating liquid comprising a filler, a polyimide precursor or a polyamideimide precursor, an organic polar solvent, and a polyoxyethylene alkylphenyl ether-modified silicone.

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